CN102924210B - Conversion method of C4 and heavier components - Google Patents
Conversion method of C4 and heavier components Download PDFInfo
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- CN102924210B CN102924210B CN201210257540.9A CN201210257540A CN102924210B CN 102924210 B CN102924210 B CN 102924210B CN 201210257540 A CN201210257540 A CN 201210257540A CN 102924210 B CN102924210 B CN 102924210B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a conversion method of C4 and heavier components, such that yields of ethylene and propylene can be improved. According to the method, C4 and heavier components separated from reaction gas are subjected to further cracking, wherein a catalyst adopted in cracking is the same with a catalyst adopted by a main reaction. The cracking device comprises an auxiliary reactor and/or an auxiliary regenerator. With the method, a total selectivity of ethylene and propylene can be improved to 85-90%, and a weight ratio of ethylene to propylene in a product can be flexibly adjusted within a range of 1.2-0.8.
Description
The application is application number: 200810140897.2, and the applying date is: 2008.7.26, and name is called the division of a kind of carbon four and the more method for transformation of heavy constituent.
Technical field:
The present invention relates to a kind of with oxygenatedchemicals (mainly methyl alcohol, ethanol, dme, C
4~ C
10alkylol cpd or its mixture etc.) be raw material, generate with low-carbon alkene be mainly generate logistics (mainly ethene and propylene) successive reaction and regenerative process in, by product carbon four and more heavy constituent (C
4 +) further method of reacting preparing ethylene and propylene.
Background technology:
Light olefin (ethene, propylene, divinyl) and light aromatics (benzene,toluene,xylene) are the basic raw materials of petrochemical complex.Current ethylene production mainly relies on the tube furnace steam cracking technique of light naphthar raw material.Due to the shortage of crude resources and the raising day by day of price, naphtha resource has more and more seemed not enough, and the production cost of low-carbon alkene is more and more higher.The ethylene production route that positive active development raw material sources are abundanter both at home and abroad, organic oxygen-containing compound raw material is through the katalysis of metal-modified SAPO type aperture phosphorus pure aluminium silicate Zn-Al-P-Si-oxide molecular sieve, can generate based on the reaction product of ethene, propylene, just be subject to both domestic and externally paying attention to widely, be in industrialization phase.
The oxygen-containing organic compound being representative with methyl alcohol or dme is typical oxygen-containing organic compound, produces primarily of synthetic gas that is coal-based or Sweet natural gas base.To be raw material production mainly contain the MTO technology of American UOP company based on the low-carbon alkene technique of ethene and propylene to the oxygen-containing organic compound being representative in order to methyl alcohol at present that (main patent is US Patent No. P6166282, USP5744680; Chinese patent ZL00137259.9), (main patent is USP6673978, USP6717023, USP6613950 for the MTO technology of ExxonMobil company of the U.S.; Chinese patent ZL00815363.2, ZL00802040.x, ZL03821995.6), the DMTO technology (ZL96115333.4, ZL92109905.3) of MTP technique (EP0448000A, DE233975A1) and the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences.
The reaction characteristics of oxygenatedchemicals (current typical case adopt be methyl alcohol) preparing low-carbon olefins technique (MTO) is rapid reaction, strong heat release and alcohol agent is lower frequently, is to carry out reacting and regenerating in the dense fluidized bed bioreactor of continuous print reaction-regeneration.Reaction generate the high-temperature oil gas being rich in the low-carbon alkene such as ethene and propylene, need to carry out chilling and washing, remove wherein catalyzer and cooling after, be sent to bottom olefin separation system and be separated.The object product of MTO process unit is ethene and propylene, byproduct liquefied gas, C
5above component and fuel gas, wherein C
4 +carbon base absorption rate be about 10%.How this part low value product is converted into ethene and the propylene of high added value, be the problem of pendulum in face of vast scientific research and project planner always.
In recent years, " MTO technology (MTO) " has become the focus and emphasis of insider's research.People conduct extensive research from aspects such as work flow, catalyzer, processing condition and device structures and explore, and obtain gratifying achievement, but about how by the byproduct C in MTO process products
4and heavier component (C
4 +) be converted into the ethene of high added value and propylene bibliographical information few.
WO200320667 patent discloses a kind of OTO technique, this invention describes two or more zeolite catalyst, the first catalyzer is ZSM-5, and the second catalyzer is the molecular sieve (ZSM-22, ZSM-23, ZSM-35, ZSM-48 etc.) of 10 rings.ZSM-5 can be considered as modification, P Modification or steam modification, micro pore volume is not less than 50% (compared with the ZSM-5 without steam modification).Oxygen-containing compound material respectively in two independently reactor with these two kinds of catalyst exposure.Oxygenatedchemicals and the first catalyst exposure form olefin product, and isolating butene content in the logistics containing butylene minimum is 20w%, and itself and the second catalyst exposure are formed the second olefin product.
US604917, US20040102667 and US5914433 patent all relates to during low-carbon alkene is produced the technique improving ethene and productivity of propylene.By C in product
4alkene, C
4 +alkene or heavier hydrocarbon components transform, and greatly can improve the productive rate of ethene and propylene.
The technique that US604917 patent relates to may be used for ethylene unit, catalytic cracking unit and MTO process unit.After ethene and propylene separation being reclaimed, the heavy hydrocarbon of some residual can be got back to reaction zone and transform further, or carries out the derived product that oligomerisation obtains high value.
US20040102667 patent relates to the technology that OTO technique improves ethene and productivity of propylene.Adopt silicon aluminium phosphate catalyst.The C that product is isolated to
4~ C
7middle matter olefin fraction carries out cracking in an independent cracking of olefins reactor.Key step is: (1) will be rich in the charging C of alkene
2~ C
8send into flash trapping stage device, separate C
2~ C
3light olefin and C
4 +heavy olefin fraction; (2) olefin fraction will be weighed and send into the second-order separation district, separate the second light olefin fraction, C
4~ C
7middle matter olefin fraction and C
7 +heavy olefin fraction; (3) middle matter olefin fraction is sent into cracking of olefins reactor, make crack materials at least partially be C
2~ C
3alkene; (4) C of cracking formation
2~ C
3alkene some get back to the second-order separation district.Another part is drawn out of; (5) the second light olefin fraction of distinguishing of the second-order separation some turn back to flash trapping stage district.
US5914433 patent relates to the technique that OTO produces polymer grade olefin.Be characterized in carrying out cracking to the mixed butene in product and heavy constituent, thus improve the output of ethene and propylene.Cracking reaction is carried out in riser cracking district or the independent zone of cracking, provides handiness to technique.This technique overcomes the equilibrium-limited of silicon aluminium phosphate catalyst, also improves the life-span of catalyzer, improves the stability of catalyzer at zone of transformation.
Main processing step is: (1) oxygenatedchemicals (C
1~ C
4a kind of alcohol or a kind of ether) raw material thinner dilutes, adopt silicon aluminium phosphate catalyst (SAPO-34, SAPO-17 or its mixture) and fluidized-bed reactor, obtain Light olefin products logistics at reaction conditions; (2) ethene, propylene and mixed butene heavy constituent is obtained after stream of light olefins being separated; (3) take out reclaimable catalyst at least partially to go to regenerate; (4) the catalyzer part after regeneration turns back to fluidized bed reaction zone, and another part mixes with a certain amount of mixed butene and heavy constituent, enters cracking case and obtains the second product stream, generate extra ethene and propylene; (5) part second product stream is turned back to fluidized bed reaction zone.
The patent CN1803738A of American UOP company discloses to use mobile technology and independently weigh alkene interconversion procedures and oxygenatedchemicals is converted into propylene.These patent main points establish two reaction zones, and first moving bed reaction district uses the dual-function catalyst with SAPO and ZSM function, and oil gas product mainly propylene, has a small amount of ethene, butylene and C simultaneously
4 +alkene, C
1~ C
4stable hydrocarbon, a small amount of aromatic hydrocarbon and water.Reaction oil gas chilling is divided into the steam being rich in propylene, the aqueous phase comprising unreacted methyl alcohol and newly-generated oxygenatedchemicals after being separated, comprises liquid hydrocarbon three part of heavier hydro carbons (alkene, stable hydrocarbon, aromatic hydrocarbons).Recovery part water generation reaction is as the absorption agent of reaction raw materials.Second reaction zone is also moving-bed, ZSM, SAP0 dual-function catalyst using portfolio ratio different, and temperature of reaction is higher than the first reaction zone more than 15 DEG C, and object is by C
4 +conversion of olefines is propylene is main product, estimates to be similar to disclosed Atofina company OCP C
4 +olefin conversion process catalyzer.What the first reactor generated contains ethene, butylene and C
4 +alkene, C
1~ C
4the gas-phase product of stable hydrocarbon, a small amount of aromatic hydrocarbon is separated further, wherein C
4 +alkene removes the further conversion of olefines of the second reactor.
The patent CN1419527A of ExxonMobil company of the U.S. discloses C in a kind of oxygenate conversion reaction
4 +and more heavies stream, to the control method of the conversion of light product, is a kind of when not making to leave from the product stream leaving the first reaction zone the method that the heavy conversion of olefines existed in the product stream of the first reaction zone becomes carbonaceous sediment on light olefin and catalyzer when separating heavy alkene.Described method comprises: produce and leave the product stream of the first reaction zone, described in leave the first reaction zone product stream comprise heavy alkene; The product stream leaving the first reaction zone is made to move to second reaction zone when not being separated described heavy alkene from the product stream leaving the first reaction zone; With the product stream making to leave the first reaction zone under the condition that can form light olefin with catalyst exposure, described contact cause described catalyzer at least partially on form carbonaceous sediment.
The patent US4433188 of BASF AG discloses a kind of methanol/dimethyl ether alkene technology, and this invention adopts borosilicate catalyzer, comprises two-stage reaction and two-phase seperation.Material benzenemethanol/dme in first paragraph reaction zone with catalyst exposure generation catalytic cracking reaction, product separates C through the first separation system
2~ C
4alkene and C
1~ C
4alkane, remaining C
5 +component enters second reaction zone and catalyst exposure generation scission reaction, and product, through the second separation system Arene removal component, then returns the first separation system.The principal feature of this patent is circulation C
5 +component reacts under different conversion zones and condition from raw material.
The patent CN1962573A of Tsing-Hua University discloses method and the reactor of catalytic cracking for producing propylene using fluid bed, and this invention belongs to alcohol, ether cracking propylene technical field, it is characterized in that, the C in the product of low-carbon alkene preparation technology
2and C
2following component, C
4and C
4after above component is separated with object product propylene, circulation turns back to alkene in fluid catalytic cracking reaction unit and turns reaction zone and carry out conversion of olefines, and by red-tape operati condition, highly selective produces propylene.C
2 -, C
4 +two bursts of logistics had before returning to olefin reaction district speeds to put on a small quantity, accumulates to avoid inert component.Correspondingly, the multicompartment fluidized bed structure of reactor that can be used as main reaction region or olefin reaction district is proposed.This invention has propylene and always receives high, that selectivity is strong advantage.
In sum, although to relate in some oxygenate conversion reaction carbon four and more heavy constituent (C in prior art
4 +) freshening method, but also there is many problems: comprising using different catalyst systems, need to build the higher C of independently output investment ratio
4 +cracking unit, olefin cracking system thermal is uneven, and needing specially is C
4 +cracker provides required heat, and cracking condition is restricted, and transformation efficiency is lower; Only pay close attention to C in unconverted raw material and product
5 +component, does not relate to the freshening problem of butylene usually; Also have the technology of part for the purpose of propylene to improve propylene total recovery by by product circulation, but majority adopt simple form by product being looped back former reactor, etc.
Summary of the invention:
Object of the present invention is just to provide a kind of by carbon four in transforming oxygenated organic compound alkene resultant and more heavy constituent (C
4 +) be cracked into C further
2 =~ C
3 =method, to improve the selectivity of low-carbon alkene, operation conditions optimization, simplification of flowsheet, reduce construction investment.
The invention provides the method for transformation of a kind of carbon four and more heavy constituent, it is characterized in that: the reaction gas of main reactor is separated through separation system, isolated carbon four and more heavy constituent enter auxiliary reactor and the regenerated catalyst contact reacts from assisted Regeneration device, the reaction gas of auxiliary reactor and the reaction gas of main reactor are delivered to separation system together and are separated, in auxiliary reactor, the reclaimable catalyst of carbon distribution enters assisted Regeneration device after stripping, enter auxiliary reactor after coke burning regeneration to recycle, assisted Regeneration device is incorporated into from main regenerator overhead regenerated flue gas out, wherein auxiliary reactor is identical with main reactor used catalyst, the temperature of reaction of auxiliary reactor 500 ~ 650 DEG C, preferably 550 ~ 600 DEG C, reaction pressure 0.1 ~ 0.5MPa, preferably 0.1 ~ 0.3MPa, agent/expect than the weight ratio of catalyzer and carbon four and more heavy constituent (in the auxiliary reactor) 0.5 ~ 20, preferably 5 ~ 15.The temperature of assisted Regeneration device 550 ~ 750 DEG C, preferably 650 ~ 700 DEG C.
The present invention also provides the method for transformation of a kind of carbon four and more heavy constituent, it is characterized in that: the reaction gas of main reactor is separated through separation system, isolated carbon four and more heavy constituent enter auxiliary reactor and the regenerated catalyst contact reacts carrying out autonomous revivifier, the reaction gas of auxiliary reactor and the reaction gas of main reactor are delivered to separation system together and are separated, in auxiliary reactor, the reclaimable catalyst of carbon distribution all enters main reactor after stripping, or a part enters main reactor, another part enters main revivifier and mixes with the reclaimable catalyst from main reactor and carry out coke burning regeneration, catalyzer after regeneration enters auxiliary reactor again and recycles, the temperature of reaction of auxiliary reactor 500 ~ 650 DEG C, preferably 550 ~ 600 DEG C, reaction pressure 0.1 ~ 0.5MPa, preferably 0.1 ~ 0.3MPa, agent/expect than the weight ratio of catalyzer and carbon four and more heavy constituent (in the auxiliary reactor) 0.5 ~ 20, preferably 5 ~ 15.The temperature of main revivifier 550 ~ 750 DEG C, preferably 650 ~ 700 DEG C, wherein said auxiliary reactor is fluidized-bed reactor.
The present invention provides the method for transformation of a kind of carbon four and more heavy constituent in addition, it is characterized in that: the reaction gas of main reactor is separated through separation system, isolated carbon four and more heavy constituent enter auxiliary riser line reactor and the regenerated catalyst contact reacts carrying out autonomous revivifier, the reaction effluent of auxiliary riser line reactor is divided into two portions, the part accounting for auxiliary riser line reactor total reaction effluent 10 ~ 50 % by weight enters the close phase section at distance 0 ~ 6 meter, main reactor close phase section top, the another part accounting for auxiliary riser line reactor total reaction effluent 50 ~ 90 % by weight enters in the middle part of the transition section of the close phase pars infrasegmentalis of main reactor, the reaction product of main reactor is separated, reaction gas after separation is from main reactor Base top contact, the reclaimable catalyst of the carbon distribution after separation carries out coke burning regeneration recycle through the laggard revivifier of becoming owner of of stripping, the temperature of reaction of auxiliary riser line reactor 500 ~ 650 DEG C, preferably 550 ~ 600 DEG C, reaction pressure 0.1 ~ 0.5MPa, preferably 0.1 ~ 0.3MPa, agent/expect than the weight ratio of catalyzer and carbon four and more heavy constituent (in the auxiliary riser line reactor) 0.5 ~ 20, preferably 5 ~ 15.The temperature of main revivifier 550 ~ 750 DEG C, preferably 650 ~ 700 DEG C.
Oxygenatedchemicals of the present invention can be selected from methyl alcohol, ethanol, dme and C
4~ C
10in the oxygen-containing organic compounds such as alkylol cpd one or more.
The method for transformation of carbon four of the present invention and more heavy constituent is applicable to all richnesses and produces C
4 +the full scale plant of alkene, is especially applicable to catalytic cracking unit and deriving device, the MTO process unit of methanol-to-olefins, the MTP device of preparing propylene from methanol, the MTA device of Methanol aromatic hydrocarbons of oil refining process, is preferably applied to MTO process unit.
Compared to the prior art method provided by the present invention has the superiority of the following aspects:
(1) oxygen-containing compound conversion to produce olefine process unit adopts the first method for transformation of the present invention, namely during two cover reaction regeneration devices, in assisted Regeneration device, introduced the regenerated flue gas being rich in carbon monoxide by main revivifier, utilize CO burning liberated heat, improve C
4 +the temperature of olefin cracking revivifier, can meet C
4 +heat required for olefin cracking reaction, makes C
4 +olefin cracking reaction can be carried out under the operational condition optimized;
(2) method of the present invention is adopted, because the further cracking unit of its carbon four and more heavy constituent is relatively independent, carbon four and more heavy constituent conversion reaction are carried out in different reactors from raw material scission reaction, independently can control temperature and the space velocity conditions of conversion of olefines, the catalyst type that each reaction is used is simultaneously identical, avoids because catalyzer is different and causes catalyst contaminant problems.
(3) method of the present invention is adopted, by by the by product carbon four of oxygen-containing compound conversion to produce olefine technique and more heavy constituent further cracking in the method for the invention, the overall selectivity of ethene and propylene can be brought up to 85 ~ 90%, ethene adds propylene and improves 4 ~ 6 percentage points to the carbon base absorption rate of methanol feedstock, by changing operational condition, in product, ethene and propylene weight ratio can regulate between 1.2 ~ 0.8.
(4) adopt method of the present invention, the further cracker of oxygen-containing compound conversion to produce olefine process unit and its by product carbon four and more heavy constituent shares a set of chilling and water wash system, simplifies technical process, reduces construction investment.
(5) the oxygenatedchemicals scission reaction described in the present invention is thermo-negative reaction, and temperature of reaction is lower, agent/expect smaller.In the present invention, second is serial operation with the catalyst circulation pattern described in the third method, can guarantee that oxygenatedchemicals carries out under the operational condition optimized.
Below in conjunction with the drawings and specific embodiments, the present invention is described further.But do not limit the scope of the invention.
Accompanying drawing explanation
Fig. 1 is a kind of schematic flow sheet of the present invention.
Fig. 2 is the second schematic flow sheet of the present invention.
Fig. 3 is the third schematic flow sheet of the present invention.
In figure: 1-main reactor reaction gas; 2-main reactor cyclonic separator;
3-oxygenatedchemicals; 4-main reactor;
The main revivifier of 5-; 6-regenerated flue gas;
The main revivifier cyclonic separator of 7-; The reaction gas of 8-auxiliary reactor 11;
9-auxiliary reactor cyclonic separator; 10-carbon four and more heavy constituent;
11-auxiliary reactor; 12-stripping stage to be generated;
13-assisted Regeneration device riser tube to be generated; 14-assisted Regeneration device;
The regenerated flue gas of 15-assisted Regeneration device 14; 16-preheating main air;
17-main reactor stripping stage; 18-auxiliary riser line reactor;
19-auxiliary reactor regeneration riser tube; The main revivifier of 20-riser tube to be generated;
21-main reactor regeneration riser tube; 22-reaction gas;
The close phase section of 23-; The main revivifier stripping stage of 24-;
25-transition section.
Embodiment
Fig. 1, Fig. 2 and Figure 3 shows that for oxygenatedchemicals olefin process schematic flow sheet.
Figure 1 shows that two cover reaction regeneration devices, but auxiliary reactor 11 is identical with used catalyst in main reactor 4.Oxygenatedchemicals 3 is entered by main reactor 4 bottom, react with the catalyst exposure in main reactor 4, resultant of reaction is separated through main reactor cyclonic separator 2, the main reactor reaction gas 1 being rich in the low-carbon alkene such as ethene and propylene after separation is by main reactor 4 Base top contact, mix with the reaction gas 8 by auxiliary reactor 11 auxiliary reactor 11 out, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is separated, then the separation of olefins unit at rear portion is delivered to.In separation of olefins unit, reaction gas is separated, the object product ethene obtained and propylene go out device, isolated carbon four and more heavy constituent 10 enter auxiliary reactor 11 with vapor mode after preheating, directly contact with the high-temperature regenerated catalyst from assisted Regeneration device 14 in auxiliary reactor 11, react rapidly at catalyst surface, the reaction gas 8 of auxiliary reactor 11 is drawn after the catalyzer that auxiliary reactor cyclonic separator 9 removes entrained with, after mixing with the main reactor reaction gas 1 from main reactor 4 top, deliver to rear pre-separation together and olefin separation system is separated, obtain the object such as ethene and propylene product.
In auxiliary reactor 11, after reaction, the reclaimable catalyst of carbon distribution enters stripping stage 12 stripping to be generated, the reaction gas that removing reclaimable catalyst carries, reclaimable catalyst after stripping enters assisted Regeneration device riser tube 13 to be generated after guiding valve to be generated, assisted Regeneration device 14 is entered under the conveying of nitrogen, in assisted Regeneration device 14, contact coke burning regeneration with preheating main air 16, the catalyzer after regeneration enters auxiliary reactor 11 through auxiliary reactor regeneration riser tube 19 and recycles.
Regenerated flue gas 6 full dose carrying out autonomous revivifier 5 is incorporated in assisted Regeneration device 14, is rich in CO (carbon monoxide converter) gas, utilizes CO burning liberated heat to carry out supplementary C in regenerated flue gas 6
4 +heat required for olefin cracking reaction, controls CO burning with preheating main air 16 simultaneously, and the rate of combustion of carbon monoxide strictly controls by the oxygen level in the regenerated flue gas 15 of assisted Regeneration device 14, makes regenerated catalyst temperature in required scope.The pre-heating mean of main air can be selected from electrical heating method and set up interior heat collector heating main air method etc., preferred second method at revivifier.The regenerated flue gas 15 of assisted Regeneration device 14 is by smoke stack emission air.
Auxiliary reactor described in Fig. 1 and assisted Regeneration device are fluidized-bed pattern, can be bubbling bed, turbulent bed or fast bed streaming mode, preferred Turbulent Fluidization operational stage.
Figure 2 shows that main reactor 4 and the reclaimable catalyst in auxiliary reactor 11 carry out the form regenerated in same main revivifier 5, auxiliary reactor 11 is fluidized-bed.Oxygenatedchemicals 3 is entered by main reactor 4 bottom, react with the catalyst exposure in main reactor 4, resultant of reaction is separated through main reactor cyclonic separator 2, the main reactor reaction gas 1 being rich in the low-carbon alkene such as ethene and propylene after separation is by main reactor 4 Base top contact, mix with the reaction gas 8 by auxiliary reactor 11 auxiliary reactor 11 out, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is separated, then the olefin separation system at rear portion is delivered to.In separation of olefins unit, reaction gas is separated, obtain object product ethene and propylene goes out device, isolated carbon four and more heavy constituent 10 enter auxiliary reactor 11 with vapor mode after preheating, with the regenerated catalyst contact reacts carrying out autonomous revivifier 5 in auxiliary reactor 11, the reaction gas 8 of auxiliary reactor 11 is drawn after the catalyzer that auxiliary reactor cyclonic separator 9 removes entrained with, after mixing with the main reactor reaction gas 1 from main reactor 4 top, deliver to olefin separation system to be together separated, in auxiliary reactor 11, the reclaimable catalyst of carbon distribution carries out stripping at stripping stage 12 to be generated, the reaction gas that removing reclaimable catalyst carries, a reclaimable catalyst part after stripping enters main reactor regeneration riser tube 21, main reactor 4 is entered under the conveying of 1.0Mpa steam, continuation and oxygen-containing compound material 3 react.All the other nitrogen or other media (as, process air) conveying under enter into main revivifier 5 through main revivifier riser tube to be generated 20, the reclaimable catalyst of main reactor 4 through the laggard main revivifier 5 of main reactor stripping stage 17 stripping, respectively from two strands of reclaimable catalysts coke burning regeneration in main revivifier 5 of main reactor 4 and auxiliary reactor 11.Catalyzer after regeneration enters main revivifier stripping stage 24 stripping, and the regenerated catalyst after stripping turns back to auxiliary reactor 11 through auxiliary reactor regeneration riser tube 19 and recycles.The regenerated flue gas 6 of main revivifier 5 removes after the most of catalyzer carried through main revivifier cyclonic separator 7 and enters air by main revivifier 5 top.
Auxiliary reactor described in Fig. 2 is fluidized-bed pattern, can be bubbling bed, turbulent bed or fast bed streaming mode, preferred Turbulent Fluidization operational stage.
As shown in Figure 3, oxygenatedchemicals 3 is entered by main reactor 4 bottom, react with the catalyst exposure in main reactor 4, the reaction gas 22 being rich in the low-carbon alkene such as ethene and propylene after the catalyzer that main reactor cyclonic separator 2 removes entrained with by main reactor 4 Base top contact, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is separated, then delivers to the olefin separation system at rear portion.In separation of olefins unit, reaction gas 22 is separated, the object product ethene obtained and propylene go out device, isolated carbon four and more heavy constituent 10 enter auxiliary riser line reactor 18 with vapor mode after preheating, react with the catalyst exposure entered by main revivifier 5, the reaction effluent of auxiliary riser line reactor 18 is divided into two portions, the part accounting for auxiliary riser line reactor 18 total reaction effluent 10 ~ 50 % by weight enters the close phase section at distance 0 ~ 6 meter, main reactor 4 close phase section 23 top, the another part accounting for auxiliary riser line reactor 18 total reaction effluent 50 ~ 90 % by weight enters in the middle part of the transition section 25 of the close phase pars infrasegmentalis of main reactor 4, the reaction product of main reactor 4 is separated through main reactor cyclonic separator 2, reaction gas 22 after separation is from main reactor 4 Base top contact, then chilling water wash system is delivered to.The reclaimable catalyst of the carbon distribution after separation enters main reactor stripping stage 17 stripping, the reaction gas that removing reclaimable catalyst carries, and the reclaimable catalyst after stripping enters main revivifier 5 under the conveying of nitrogen, coke burning regeneration in main revivifier 5.Catalyzer after regeneration enters main revivifier stripping stage 24 stripping, and the regenerated catalyst after stripping enters auxiliary riser line reactor 18 and recycles.
On the upper, middle and lower that the injection phase of carbon four and more heavy constituent 10 is selected from auxiliary riser line reactor 18 and oxygenate feedstock pipeline, the top of preferred auxiliary riser line reactor 18 or bottom.
The regenerated flue gas 6 of main revivifier 5 removes after the most of catalyzer carried through main revivifier cyclonic separator 7 and enters air by main revivifier 5 top.
Claims (2)
1. the method for transformation of a carbon four and more heavy constituent, it is characterized in that: the reaction gas of main reactor is separated through separation system, isolated carbon four and more heavy constituent enter auxiliary riser line reactor and the regenerated catalyst contact reacts carrying out autonomous revivifier, the reaction effluent of auxiliary riser line reactor is divided into two portions, the part accounting for auxiliary riser line reactor total reaction effluent 10 ~ 50 % by weight enters the close phase section at distance 0 ~ 6 meter, main reactor close phase section top, the another part accounting for auxiliary riser line reactor total reaction effluent 50 ~ 90 % by weight enters in the middle part of the transition section of the close phase pars infrasegmentalis of main reactor, the reaction product of main reactor is separated, reaction gas after separation is from main reactor Base top contact, the reclaimable catalyst of the carbon distribution after separation carries out coke burning regeneration through the laggard revivifier of becoming owner of of stripping, catalyzer after regeneration enters auxiliary riser line reactor again and recycles, the temperature of reaction of auxiliary riser line reactor 500 ~ 650 DEG C, reaction pressure 0.1 ~ 0.5MPa, agent/material is than 0.5 ~ 20, the temperature of main revivifier 550 ~ 750 DEG C, described carbon four and more heavy constituent are from preparing low-carbon olefin from oxygen-containing compounds product, and described dose/material is than the weight ratio for catalyzer in auxiliary riser line reactor and carbon four and more heavy constituent.
2. method for transformation according to claim 1, is characterized in that: the temperature of reaction of auxiliary reactor 550 ~ 600 DEG C, reaction pressure 0.1 ~ 0.3MPa, and agent/material is than 5 ~ 15; The temperature of main revivifier 650 ~ 700 DEG C, described dose/material is than the weight ratio for catalyzer in auxiliary riser line reactor and carbon four and more heavy constituent.
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